Multimetallic assembly, methods of making multimetallic assembly, methods of oxidizing water, methods of O-atom transfer catalysts, and methods of carbon dioxide reduction

Abstract

Embodiments of the present disclosure provide for multimetallic assemblies, methods of making a multimetallic assembly, methods of oxidizing water, methods of O-atom transfer catalysis, and the like.

At least the following is claimed: 
     
       1. A multimetallic assembly, comprising the following structure: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein Z is NH, NR, O, S, CH, CR, or CH 2 ; R and R′ are independently selected from an alkyl group, an aryl group, NO 2 , H, a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, a sulfonate, a sulfonyl ester, a carboxylate, an ester, CF 3 , OMe, or COOR 1 ; A is CH or N; R 1  and R 2  are independently selected from H, alkyl group, an aryl group, a carboxylate, NO 2 , a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, sulfone, sulfonate, a sulfonyl ester, a carboxylate, CF 3 , OMe, or ester. 
       
     
     
       2. The multimetallic assembly of  claim 1 , wherein: 
       
         
           
           
               
               
           
         
       
     
     
       3. The multimetallic assembly of  claim 1 , wherein: 
       
         
           
           
               
               
           
         
       
     
     
       4. The multimetallic assembly of  claim 1 , wherein one or more metals are associated with the multimetallic assembly. 
     
     
       5. The multimetallic assembly of  claim 2 , wherein the metal is a transition metal. 
     
     
       6. The multimetallic assembly of  claim 2 , wherein the metal selected from the group consisting of: manganese, iron, cobalt, nickel, copper, vanadium, chromium, palladium, platinum, gold, ruthenium, rhodium, and iridium. 
     
     
       7. A method of oxidizing water, comprising:
 exposing the water to a multimetallic assembly having the following structure: 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein Z is NH, NR, O, S, CH, CR, or CH 2 ; R and R′ are independently selected from an alkyl group, an aryl group, NO 2 , H, a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, a sulfonate, a sulfonyl ester, a carboxylate, an ester, CF 3 , OMe, or COOR 1  ; A is CH or N; R 1  and R 2  are independently selected from H, alkyl group, an aryl group, a carboxylate, NO 2 , a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, sulfone, sulfonate, a sulfonyl ester, a carboxylate, CF 3 , OMe, or ester. 
       
     
     
       8. The multimetallic assembly of  claim 7 , wherein: 
       
         
           
           
               
               
           
         
       
     
     
       9. The multimetallic assembly of  claim 7 , wherein: 
       
         
           
           
               
               
           
         
       
     
     
       10. The multimetallic assembly of  claim 7 , wherein one or more metals are associated with the multimetallic assembly. 
     
     
       11. The multimetallic assembly of  claim 10 , wherein the metal is a transition metal. 
     
     
       12. The multimetallic assembly of  claim 10 , wherein the metal selected from the group consisting of: manganese, iron, cobalt, nickel, copper, vanadium, chromium, palladium, platinum, gold, ruthenium, rhodium, and iridium. 
     
     
       13. A method of reducing carbon dioxide, comprising:
 exposing the carbon dioxide to a multimetallic assembly having the following structure: 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein Z is NH, NR, O, S, CH, CR, or CH 2 ; R and R′ are independently selected from an alkyl group, an aryl group, NO 2 , H, a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, a sulfonate, a sulfonyl ester, a carboxylate, an ester, CF 3 , OMe, or COOR; A is CH or N; R 1  and R 2  are independently selected from H, alkyl group, an aryl group, a carboxylate, NO 2 , a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, sulfone, sulfonate, sulfonyl esters, carboxylate, or ester. 
       
     
     
       14. A method of O-atom transfer, comprising:
 exposing O 2  or a reactive oxygen species to a multimetallic assembly having the following structure: 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein Z is NH, NR, O, S, CH, CR, or CH 2 ; R and R′ are independently selected from an alkyl group, an aryl group, NO 2 , H, a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, a sulfonate, a sulfonyl ester, a carboxylate, an ester, CF 3 , OMe, or COOR 1 ; A is CH or N; R 1  and R 2  are independently selected from H, alkyl group, an aryl group, a carboxylate, NO 2 , a substituted alkyl, a cycloalkyl, a substituted cycloalkyl, a substituted aryl, a heteroaryl, a substituted heteroaryl, sulfone, sulfonate, a sulfonyl ester, a carboxylate, CF 3 , OMe, or ester; 
         reacting the product of step one with an electron-rich substrate to transfer the O-atom to the electron-rich substrate.